KR970000745B1 - Coloring material for antibiotic cosmetics, method for their preparation and cosmetic compositions containing coloring material - Google Patents

Abstract

An amorphous glassy metal oxide was coated on the inorganic pigment surface, and an antibiotic metal or metal ion was simultaneously mixed and solidified in the skeletal structure of the metal oxide composite coating layer to give the pigment for antibiotic cosmetics. The inorganic pigment, such as silica, talc, kaolin, mica, aluminium oxide, barium sulfate, titanium dioxide, boron nitrate, aluminium silicate, magnesium oxide and chromium hydroxide etc. has 0.1- 50um of average diameter.

Description

Antimicrobial cosmetic pigments and preparation method thereof and cosmetic composition containing same

The present invention relates to an antimicrobial pigment, a method for manufacturing the same, and a cosmetic composition containing the same, and more particularly, to form an amorphous coating layer of glass on the surface of a cosmetic pigment, wherein the antimicrobial cosmetic pigment is made by solidifying an antimicrobial metal in a bonding grid. It relates to a manufacturing method and a cosmetic composition containing the same.

The purpose of the addition of antiseptic fungicides in cosmetics is to sterilize microorganisms derived from raw materials or manufacturing or filling, or to contaminate microorganisms contaminated when used by consumers, and to prevent proliferation by preventing microorganisms from being deteriorated, odors and molds.

Antiseptic disinfectants used in cosmetics include formic acid, glutaldehyde, chlorohexidine gluconate and dihydrochloride, dimethyloxazolidine, dimethic acid, dibrominated hexamidine and its salts, and diazolidinyls as described in the Cosmetics Standards. Urea, DMDMHydantoin, 2,4-dichlorobenzyl alcohol, 3,4-dichlorobenzyl alcohol, dihydroacetic acid and salts thereof, sodium lauroyl sarcosine, methenamin-3-chloroallylochloride, inorganic sulfides and The salts thereof, lauroyl sarcosine sodium, methenamin-3-chloroallylochloride, inorganic sulfides and hydrogen sulfides, benzyl alcohol, benzyl hemiformal, borax, 5-bromo-5-nitro-1,3 -Dioxane, 2-bromo-2-nitropropane-1,3-diol, brominated alkylisoquinolinium, bromochlorophene, biphenyl-2-ol (O-phenylphenol) and salts thereof, 1,3 Bis (hydroxymethyl) -5,5-dimethylimidazolidine-2,4-dione, salicylic acid and the like Acids, phenyl salicylate, sodium iodo date, sorbic acid and its salts, zinc-rich blood-one, benzoic acid and its salts, alkyl (C ₁₂ -C ₂₂₎ tree methyl bromide and chloride, MD emhi hydantoin, HCl to the diamino alkyl hit Glycine solution (30%), benzetonium chloride, benzalkonium chloride, undecylenic acid and its salts and monoethanolamide, imidazolidinyl urea, isopropylmethylphenol, isopropylcresol, chiram, captan, quiternium-15, Quinolin-8-ol and its salts, 5-chloro-2-methyl-isothiazol-3 (2H) -one and 2-methylisoazole-3 (2H), are mixtures, chlorobutanol, chloroacetamide, p -Chloro-m-cresol, chloroxylenol, chlorophenesin, chlorophen, 1- (4-chlorophenoxy) -1- (imidazol-1-yl) 3,3-dimethylbutan-2-one, Tetrabromo-o-cresol, trichromic acid, triclocarbine, paraoxybenzoic acid ester, phenoxyethanol, phenoxyisopropanol, phenol, o- Nylphenol, formaldehyde and paraformaldehyde, poly (1-hexamethylene biguanide hydrochloride), propionic acid and its salts, pyroxtoneolamine, pyridin-2-ol, 1-oxide, hexamethylenetetraamine, hexeti Dine, hexatidine and salts thereof, N- (hydroxymethyl) -N- (dihydroxymethyl-1,3-dioxo-2,5-imidazoldinyl-4) -N '-(hydroxymethyl) Urea, 1-hydroxy-4-methyl-6 (2,4,4-trimethylpentyl) 2-pyridone, and monoethanolamine salts thereof, and the like.

However, dichlorophene, mercury and its compounds, non-allols, salicylic anhydrides, etc., are strictly prohibited because of their toxicity, despite their antiseptic effect.

In general, microorganisms including bacteria require water and nutrients to multiply. There are many raw materials used in cosmetics, and microorganisms multiply using these carbon sources. Therefore, products that do not contain water do not grow in principle even when microorganisms are attached, but may be in a spore state. However, some antimicrobial flavoring ingredients or products containing ethanol inhibit the growth of microorganisms, but the use of antiseptic disinfectants is inevitable in emulsifying products, lotions, shampoos and color products.

That is, the basic prescription of cosmetics is emulsion, solubility, or cake or powder composed of water, oil, surfactant, or powder combination, so microorganisms are easy to multiply and separate like foods, and there are odors, discoloration and mold. In addition to lowering the value of the product, it can have a adverse effect on the skin. Therefore, sterilization of bad microorganisms present on the skin keeps the skin clean, and is used in combination with preservatives and fungicides to prevent skin troubles caused by microorganisms.

However, these antiseptic fungicides regulate their usage by setting the mixing limit because of the safety they can have on the human body. For example, among the antiseptic disinfectants specified in BOSA Publication No. 1993-57, DMDMHidantoin is 2.0% (product for hair), benzoic acid and its salts are 0.5% as benzoic acid, and 1.0% for paraoxybenzoic acid ester. Formulation limits are set.

On the other hand, the factors affecting the antiseptic sterilization effect of the antiseptic disinfectant formulated in cosmetics include the pH of the cosmetic, the solubility of the antiseptic disinfectant, the combination with other antiseptics, nonionic surfactants, powders, water-soluble polymers, electrolytes, wetting agents, and containers. Materials and the like, and the antiseptic effect is affected by these factors. For example, paraoxybenzoic acid esters exhibit normal antimicrobial activity when the pH is neutral or acidic, but the antimicrobial activity is lower when alkali, and in products containing water-soluble polymers or nonionic surfactants, they adsorb paraoxybenzoic acid esters. In addition, the preservative sterilization effect is lowered because the concentration of the compound is significantly reduced by forming a complex compound. Also, the antiseptic disinfectant is adsorbed according to the powder of the product or the material of the filled container to reduce the antiseptic sterilization effect.

And antiseptic fungicides, together with the restriction of the amount of the formulation according to their own irritant concerns, the effect of pH of the cosmetic composition formulation, their solubility, the combined effect of other antiseptic fungicides, antibacterial by adsorption of the non-ionic surfactant and the water-soluble polymer used Problems such as over-blending than the amount of preservatives required by the deactivation, the effect of electrolyte and humectant, the adsorption of powder and container material, the long-term sustainability of antiseptic sterilization effect, and the stability are pointed out as problems. .

On the other hand, cosmetics other than cosmetics, antimicrobial materials other than the antiseptic fungicides have been used for the production of antimicrobial sanitary fiber, soil sterilization or water quality improvement. For example, alkali metal carbonates and zeolites (Japanese Patent Laid-Open No. 60-100504), antimicrobial fiber products (Japanese Patent Laid-Open Publication No. Hei 2-307968, Japanese Patent Laid-Open Publication Hei 3-124810) ), Ion-exchanged titanium oxide (Japanese Patent Laid-Open Publication No. 3-52804), silicate mineral (Japanese Patent Laid-Open Publication No. 3-193707), haepostone (Sepiolite, Japanese Laid-Open Patent Publication No. 3-275605), carbon (Korea Publication) Patent No. 90-3582) and heavy metal salts of hyaluronic acid (international application WO 87-05517) are known as antimicrobial agents.

However, since these antimicrobial materials are mostly used for ion exchange to support metals, they have a porosity to increase ion exchange rate and have a large surface area. As a cosmetic pigment, coarse and dense feeling, high oil absorption, and oxidation contact with oil It is not suitable because it has limitations in use due to concern, and it is pointed out as problems such as maintaining efficiency and persistence of antimicrobial effect and deactivation due to adsorption of other adsorbents.

The present inventors earnestly studied a method of easily supporting an antimicrobial metal on the surface of the cosmetic pigment to achieve a wide range of antimicrobial and bactericidal effects on microorganisms including bacteria in order to solve the various problems as described above. An amorphous glassy metal oxide coating layer was prepared on the surface of the pigment, and silver, copper, and zinc, which had an antimicrobial effect, were dissolved in the skeletal structure of the amorphous glass coating layer. The present invention has been completed by preparing an excellent antimicrobial cosmetic pigment and a cosmetic composition containing the same, and the present invention is prepared by providing a new antimicrobial cosmetic pigment having excellent antibacterial and bactericidal properties against microorganisms such as bacteria and fungi, thereby essential for cosmetics. Of unprotected or low preservative products with the use of antiseptic disinfectant The object of the present invention is to provide a cosmetic composition capable of manufacturing and preventing skin irritation caused by antiseptic fungicides blended in existing products, and having a uniform and long-lasting antibacterial effect and antiseptic effect.

Cosmetic pigments having an amorphous glassy coating layer in which the antimicrobial metal is dissolved according to the present invention, when moisture is present in the surroundings, the amorphous glassy coating layer coated on the pigment surface is gradually dissolved by the water together with the antimicrobial metal in the skeletal structure. It is released and exerts antibacterial effect. At this time, the solubility of the amorphous glass coating layer to be dissolved is similar to or lower than that of general glass or bottle glass, and thus the release concentration of the antimicrobial metals released together is in the range of several to several tens of PPI (ppb, 10- ^{). 9} ) shows the concentration below. Therefore, even at very low concentrations, the antimicrobial effect is sustained. In order to form an amorphous glassy coating layer that can effectively exhibit and control antimicrobial properties, a composite coating layer of an oxide composed mainly of silica (Sio ₂ ) is used.

When the antimicrobial cosmetic pigment of the present invention is blended into a cosmetic composition, regardless of the pH range and solubility of the cosmetic composition, it is also excellent in combination with other antiseptic fungicides, and used in micelles such as nonionic surfactants used. It does not cause the problem of lowering the activity by entering or forming a complex to reduce the concentration, and does not cause the effect of decreasing the concentration due to the adsorption of water-soluble polymers or the formation of a complex compound, and with potassium chloride, sodium pyrrolidone carbonate Cosmetics with excellent skin safety because it gives excellent antibacterial effect in a small amount without the reduction of the antibacterial effect due to the change of concentration by the same electrolyte and wetting agent such as polyethylene glycol and the adsorption phenomenon according to the powder or container material used. For the preparation of the composition, the distribution process and the Giving an excellent antimicrobial effect even for secondary glossy microorganisms that occur during the so is the resolution of a conventional cosmetic composition problem.

The antimicrobial effect of the antimicrobial metal used in the present invention has not yet been clearly identified as a mechanism, but Miller and N Geli et al. confirmed that mercury, silver, copper, platinum, iron, aluminum, zinc, magnesium, and palladium had an inhibitory effect on the growth rate of bacteria. Similar results were obtained in Bitter and Christian experiments. In particular, N Geli said that the sterilization of these metals is not due to the chemical action of the metals, but is due to the oligodynamic effect. For example, colloidal gold particles in which metals are dispersed in colloidal ultrafine powders are used for the treatment of tuberculosis and leprosy, and colloidal silver particles are widely used for the treatment of gonorrhea. It is speculated that the mechanism by which metal particulates are killed is a microscopic motion effect.

The identification of the mechanism of ultra-fine motion by ultra-fine particles has achieved tangible results as new methods using the latest technology are developed. For example, using microscopic microscopy, it was confirmed that macrophages-like cells J774.2 penetrated into the cells by phagocytosis in a medium containing silver ultrafine particles. The ultrafine particles tend to migrate to the cell division and rearrange and aggregate, and due to the aggregation phenomenon in the cell division, it is observed that macrophages do not completely divide. It is believed that silver fine particles inhibit the proliferation of cells by killing their aggregates in the cells and thereby inhibiting cell membrane separation, and this phenomenon is a result of oligodynamic action.

On the other hand, as with these metals, general metals have temperature sterilization, and the strength is mercury, silver, copper, gold, zinc, iron, lead, etc., and the solubility and dissociation degree of metal salts is known to be strong. In general, chloride, nitrate, iodide, and bromide are strong, and fluoride is highly toxic, whereas organic acid salts such as formate, acetate, and succinate have weak bactericidal properties. Therefore, the bactericidal properties of metal salts are known to be related to the properties of the anions that bind to the properties of the metals themselves.

The present invention will be described in detail as follows.

Silica, talc, kaolin, mica, cerasite, aluminum oxide, barium sulfate, zinc oxide, titanium dioxide, zirconium oxide, aluminum hydroxide, boron nitride, magnesium silicate, which are inorganic pigments for cosmetics having an average particle diameter of 0.1-50 μm It is used as a starting material for producing antimicrobial cosmetic pigments by using one or two or more selected from among aluminum, silicate, magnesium aluminum silicate, magnesium oxide, iron oxide, chromium oxide, and chromium hydroxide. A metal oxide for forming an amorphous glassy coating layer on the surface and composed of silica alone or silica (Sio ₂ ) as a main component thereof, zinc oxide (ZnO), magnesium oxide (MgO), calcium oxide (CaO), aluminum oxide (Al ₂ O _3), lithium oxide (Li ₂ O), sodium (Na ₂ O), potassium oxide (K ₂ O) and iron oxide (Fe ₂ O ₃₎ of the glass amorphous appropriately combined To prepare a coating layer. In order for the antimicrobial metal to be easily dissolved in the crystal lattice of the metal oxide composite coating layer and gradually released to the outside, silica is appropriately mixed with the above-mentioned monovalent alkali metal oxide, divalent alkaline earth metal oxide and trivalent metal oxide. It is more preferable to constitute a metal oxide composite coating layer.

The use amount of silica used in the present invention is not suitable at 40 parts by weight or less because the metal oxide composite coating layer is not formed or the hardness is increased and the solid solution capacity of the antimicrobial metal may be lowered, and the upper limit of the silica content is not limited. However, more preferably, 80 parts by weight or less is preferable. When the content is more than 80 parts by weight, the content of alkali metal and alkali metal oxide, which acts as a relatively low flux, is not high because the sintering temperature is not economical, and the antimicrobial metal is difficult to exist in a uniform solid solution.

The content of monovalent alkali metal oxide to be treated with silica is preferably 0-15.0 parts by weight. Alkaline metal oxides act as a flux during sintering and have an advantage of lowering the sintering temperature, but when contained in an amount of 15.0 parts by weight or more, the solubility of the metal oxide composite coating layer increases more than necessary, which is not preferable. The content of divalent alkaline earth metal oxide and trivalent metal oxide is 0-20.0 parts by weight, respectively, when the content of more than 20.0 parts by weight of silica is lowered because the ability to employ antimicrobial metal is bad, the antimicrobial power is not preferred.

In addition, since the composition of the metal oxide composite coating layer is substantially similar to that of glass, a small amount of transition metal oxide iron oxide can be added for coloring purposes as a method for preventing the function of the cosmetic pigment from deteriorating due to transparency due to low refractive index. have. The amount of iron oxide added is appropriately 0-3.0 parts by weight. Iron oxide not only enhances the coating power by coloring, but also provides the function as an inorganic pigment with excellent color stability depending on the content of iron oxide, and also imparts UV blocking ability due to the presence of a spectroscopic absorption band in the ultraviolet-visible wavelength range. It is suitable as a pigment for cosmetics.

In the present invention, the coating aroma of the metal oxide composite coating layer formed on the surface of the inorganic pigment for cosmetic is preferably 3.0-50.0 parts by weight based on the inorganic pigment. If it is 3.0 parts by weight or less, the antibacterial effect cannot be sufficiently exhibited, and if it is 50.0 parts by weight or more, the antibacterial effect is sufficient, but it is not preferable because the functional degradation as a cosmetic pigment, that is, the specific gravity of the pigment increases and the hardness increases, which makes the feeling of use worse.

On the other hand, as a metal used to impart antimicrobial properties, at least one selected from silver, copper, or zinc is solidified in the bonding structure of the metal oxide composite coating layer.

The antimicrobial metal content is 0.00001-5.0 parts by weight, preferably 0.00001-2.0 parts by weight, and more preferably 0.01-1.0 parts by weight with respect to the metal oxide composite coating layer.

In order to form an amorphous glassy metal oxide composite coating layer on the surface of the inorganic pigment and to solidify the antimicrobial metal in the bonding structure of the composite coating layer, the surface of the inorganic pigment is first coated with silica, and then amorphous glass material is formed thereon. Silica (SiO ₂ ) and zinc oxide (ZnO), oxide of RO type, magnesium oxide (MgO), calcium oxide (CaO), aluminum oxide (Al ₂ O ₃ ), oxide of type R ₂ O ₃ , R ₂ Lithium oxide (Li ₂ O), sodium oxide (Na ₂ O), and potassium oxide (K ₂ O), which are O-type oxides, are added together with an antimicrobial metal source, and mixed or pulverized dry or wet and sintered. At this time, the input step of the antimicrobial metal source is first coated with silica and then adsorbed onto the surface of the inorganic pigment coated with silica by coprecipitation or precipitation in the form of antimicrobial metal salt or dry or wet for the second metal oxide coating treatment. It is preferable to add during mixing and grinding. Alternatively, the same result can be obtained by adding the same to the components of the amorphous glassy metal oxide composite coating layer.

In the addition of the metal oxide and the antimicrobial metal, the metal oxide may be added as the metal oxide itself or in the form of carbonate, oxalate, sulfate or nitrate, and these salts cause redox reaction when sintered at high temperature. Is generated. Therefore, the added salts can be easily solidified in the amorphous glassy coating layer in the form of metal since the redox reaction is generally removed in the form of gas. In particular, when carbonate is used, it is more preferable because it is removed with carbon dioxide (CO ₂ ) without generating toxic gas.

The method for forming the metal oxide composite coating layer on the surface of the inorganic pigment is a method of first coating silica with neutralization titration method of sodium hydroxide, sol-gel method using silane alkoxide, and then coating metal oxide. Or direct sintering of silica with other metal oxides.

Neutralization titration method dissolves sodium silicate having a molar ratio of SiO ₂ / Na ₂ O in the range of 1-4 in purified water, heats it to a temperature of 60-80 ℃ while dispersing and stirring the coarse pigment, and then titrates with acid solution to precipitate It is a method of surface treatment of silica by making the time point of this rapid generation into an end point, filtering, washing | cleaning, and drying the produced precipitate. This method can facilitate the formation of an amorphous glassy coating layer subjected to the primary treatment of the surface of the inorganic pigment for cosmetics with silica in advance and the solid solution of the antimicrobial metal and the secondary treatment.

The sol-gel method adds silane alkoxide (Silanalkoxide) to the water phase together with an alcohol solution and an acid solution having the same carbon number as the carbon number of the corresponding alkoxide of the silane alkoxide, and the inorganic pigment is dispersed and stirred therein at 25-80 ° C. Heated to a temperature of to form a sol in which the fine particles of the metal oxide or hydroxide are dissolved by hydrolysis and polymerization of the compound in the solution, and further reacted for 30 minutes to 1 hour to gel, filter, wash and dry the surface. That's how to handle it. In the sol-gel method using a silane alkoxide, as the silane alkoxide, tetramethoxysilane (Si (OCH ₃ ) ₄ ), tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ), tetrabutoxysilane (Si (OC) ₃ H _{7) 4)} it is preferably used by selecting one kind of the way.

In the case where only silica is first coated by the neutralization titration method of sodium silicate or the sol-gel method of silane alkoxide, the coating amount of silica is preferably 1.0-15.0 parts by weight based on the inorganic pigment.

In this way, a coating layer of silica is formed on the surface of the inorganic pigment by the neutralization titration method and the sol-gel method, and then other metal oxides are weighed into dry mixture by a ball mill or the like, or by using a purified water or alcohol as a solvent, a ball mill or the like. Wet mixing (Wet milling), filtered, dried and sintered by heat treatment to form a metal oxide composite coating layer.

According to the direct sintering method, all of the high purity anhydrous silica and other metal oxides to be coated are weighed and then ground mixed with an inorganic pigment in a ball mill or the like, or wet mixed with a ball mill using purified water or alcohol as a solvent. After drying, it is sintered by heat treatment to form a metal oxide composite coating layer on the surface of the inorganic pigment.

Metals used for imparting antimicrobial properties are silver, copper, zinc, and the like. In order to solidify these metals in the metal oxide composite coating layer gap, dry mixing or heat treatment during the formation of the metal oxide coating layer described above is performed. It may be added in the process step, preferably in the form of a water-soluble salt in the wet mixing step to be doped (Dopping). In order to solidify such a metal in the skeleton of the amorphous glassy composite coating layer, ultrafine particles of the metal may be used, but by reducing the sintering operation using these salts, more uniform and fine ultrafine particles may be dissolved in the skeleton structure. For example, in the case of preparing an amorphous glassy composite coating layer, when silver nitrate solution is mixed together and sintered, silver nitrate is decomposed and reduced at a temperature of 440 ° C. or higher to produce metallic silver, and nitrate ion (NO ₃ ^−). ) Is exhausted and removed in the form of oxygen, nitrogen and nitrgen oxide. In addition, a small amount of ammonia water is added to form an ammonium chloride in order to remove residual chloride ions that cannot be removed only by washing with an acid solution in a method of treating sodium silicate, and then exhausted with a sublimable ammonium chloride gas at around 400 ° C. Can be removed. This series of operations is called roasting and is usefully used in the present invention.

In addition, when iron oxide is added, a method of adding iron oxide (Fe ₂ O ₃ ) and iron hydroxide (FeOOH) in the form of iron chloride or iron sulfate and dropping ammonia water to add them as a co-precipitate is uniformly added. It is more preferable at the point which can mix. In the precipitation or coprecipitation method, when the antimicrobial metal is added as a salt, these metal salts may be titrated with alkali, coprecipitated with a hydrate or hydroxide to uniformly dop the antimicrobial metal, and then solidified inside the metal oxide composite coating layer by sintering. It is preferable. Especially in the case of chloride salts and sulfates, the use of ammonia as the corresponding alkali produces ammonium chloride (NH ₄ Cl) or ammonium sulfate ((NH ₄ ) ₂ SO ₄ ) in addition to the desired metal hydrate, which are either sublimable or It is very suitable because it is decomposable and easily removed by the roasting process described above at a temperature of 300-500 ° C. The amount of ammonia water used is 1: 1 equivalent to the salt for the purpose of proper coprecipitation of the metal salt, and for the purpose of removing the halogen anion remaining in the neutralization titration of sodium silicate as described above or for controlling the atmosphere of the sintering furnace. It is preferable to use 0-10 parts by weight of 28% aqueous ammonia to the coated inorganic pigment.

The conditions for heat treatment for the final sintering depend on the composition and content ratio of the metal oxide composite coating layer and the type of doped antimicrobial metal, but when the content of alkali metal oxide acts as a flux and when silver is used, In the case of treating at a low sintering temperature, it is preferable to treat at a high sintering temperature when the silica content is high. Approximate sintering conditions are 10 minutes to 10 hours at a temperature of 400 ° C-1200 ° C, preferably 30 minutes to 5 hours at a temperature of 400 ° C-1000 ° C.

One of the important parameters in the heat treatment step is to control the sintering atmosphere inside the sintering furnace. That is, it is preferable to reduce the atmosphere when roasting during heat treatment, and to switch to the oxidation atmosphere when sintering to the target temperature. In the roasting process, the reducing atmosphere makes the added antimicrobial metal easy to reduce and solidify, and the oxidation atmosphere at the final sintering temperature is easy to form amorphous glassy. In order to control the reducing atmosphere of the roasting process, it is preferable to use an aqueous solution of urea ((NH ₂ ) ₂ CO) during wet mixing to prepare a metal oxide composite coating layer or through a separate input process before sintering. The sintering furnace control of the roasting process is changed to the ammonia atmosphere according to the use of ammonia, and the use of urea helps to reduce the oxidizing atmosphere inside the sintering furnace. The amount of urea used is 0 to 3.0 parts by weight based on the sintered material to be sintered. On the other hand, the method of sintering by substituting nitrogen gas for the inside of the sealed sintering furnace is most preferable among the atmosphere control methods in the sintering furnace.

The use of the antimicrobial cosmetic pigments prepared as described above can be applied to all cosmetics that can contain or combine general inorganic pigments.

Powders that can be used as general inorganic pigments include powder foundations, compacts, two-way cakes and face powders, and powders such as eye shadow, powder blush, mascara, lipstick, lip gloss, lip pencil, eyeliner and eyebrow pencil. Cosmetic products, emulsified foundations, cosmetic bases such as makeup bases, packs such as powder packs and cleansing packs, some basic products such as sunscreen creams, lotions, and lotions, and whole body products such as baby powders and body powders. Inorganic pigments formulated into these products can be contained from as little as 0.1 part by weight to as high as 100 parts by weight.

The antimicrobial cosmetic pigments of the present invention can exert an antimicrobial effect on all cosmetics to which the combination of inorganic pigments can be applied. For example, in the case of a lotion, since the ethanol component is mix | blended, the antimicrobial cosmetic pigment of this invention has sufficient antibacterial effect with the compounding quantity of 0.1 weight part or less, but the preferable compounding quantity at this time is about 0.1 weight part. In the case of powdered powder, it may also be blended at 50.0 parts by weight or more, but in this case, it is not preferable in view of exerting an antimicrobial effect. Therefore, the compounding quantity of the antimicrobial cosmetic pigment of cosmetics is 0.001-50.0 weight part, Preferably it is 0.01-30.0 weight part, More preferably, it is 0.1-20.0 weight part.

Cosmetic application of the antimicrobial cosmetic pigments of the present invention is prepared in the same manner as the manufacturing method using a general inorganic pigment, there is no disadvantage of product prescription due to the formulation of the antimicrobial cosmetic pigments in cosmetics.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.

Example 1

In 700 ml of purified water, 114 g of sodium silicate having a molar ratio of SiO ₂ / Na ₂ O of 2.4 and a water content of 50% (H ₂ O) was dissolved, and 100 g of mica having an average particle diameter of 20 μm was dispersed therein, followed by stirring at 300 rpm. Heat to ℃ and add 1.0 mole hydrochloric acid until pH reaches 7, stop the addition when sudden aggregation is observed, filter and wash several times, then carefully add 1.0 mole ammonia Adjust to 7.0. This was dried to 120 ° C. and heated to 400 ° C. to remove a small amount of chloride (Cl ⁻ ) ions used for titration of sodium silicate as ammonium chloride (NH ₄ Cl) to remove 120 g of mica coated silica. Got. 7.5 g of aluminum hydroxide (Al (OH ₃ )), 2.5 g of calcium carbonate (CaCO ₃ ) and sodium carbonate (Na ₂ CO ₃ ) were added thereto, and 1.6 g of nitrate was dissolved in 100 ml of purified water. 10 minutes, and then dried, and then heated to 450 ℃ in an electric furnace at a rate of 10 ℃ per minute to maintain the temperature at 450 ℃ for 30 minutes, and then heat treated at 800 ℃ at a temperature rising rate of 5 ℃ per minute for 1 hour The antimicrobial pigment which the metal oxide composite coating layer consists of a weight part of silica 70, aluminum oxide 12, calcium oxide 10, and sodium oxide 8 was obtained.

Test of antimicrobial effect 1

In order to test the antimicrobial effect, the sample obtained by the method of Example 1 was added to the agar medium to prepare a culture plate having a concentration of 0.05%, 0.1%, 0.5%, 1.0%, 2.0% respectively. Inoculate the test strains of E. coli, Pseudomonas aeruginosa, Staphylococcus aureus, Black mold, and Candida to 10 ⁶ cells / ml, and inoculate Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus in a culture dish containing normal mica as an antimicrobial pigment and a control group. The plate was incubated at 37 ° C. for 24 hours, and the number of bacteria was measured. The culture plate inoculated with black mold and Candida was incubated at 30 ° C. for 3 days to confirm the growth of bacteria and the minimum growth inhibitory concentration (MIC) was measured. . The results are shown in Table 1 below.

In Table 1, the-indicates that the bactericidal effect of killing the inoculated bacteria is observed, the + indicates that the inoculated bacteria continue to grow.

The antimicrobial pigment of Example 1 exhibited a growth inhibitory effect at a concentration of 0.1 to 0.5% dilution for bacteria such as Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus, and a growth inhibitory effect at concentrations of 0.5% or higher for fungi Candida and black mold, and inoculation. At all concentrations above 1.0%, the killing effect is shown, showing excellent antimicrobial effect.

Example 2

Tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) 1.0 + Purified water 1.3 + 1N HCl 0.02 + Ethanol (C ₂ H ₅ OH) Dispersed 10 g of zirconium oxide (ZrO ₂ ) in 500 ml of a mixed solution made of a weight ratio of 75.0 And stirred at room temperature (25 ° C.). The dispersion was stirred at rpm 300 with a stirrer to react with tetraethoxysilane for 50 minutes to produce silica, and then aged, filtered and dried to obtain 11.2 g of zirconium oxide coated with silica. Metal is equivalent to 0.2g in terms of 0.001g of powder, 0.1g of copper sulfate, 0.1g of magnesium oxide (MgO), calcium oxide (CaO), and 3.0g of calcium carbonate (CaCO ₃ ) and sodium oxide (NaO). After adding sodium carbonate (Na ₂ CO ₃ ), which was ground in a ball mill for 10 minutes, the temperature was raised at a rate of 10 ° C. per minute, and heat-treated at 800 ° C. for 2 hours to obtain an antimicrobial pigment.

Example 3

An antimicrobial pigment was obtained in the same manner as in Example 2, except that calcium carbonate (K ₂ CO ₃ ) was used instead of sodium carbonate in Example 2.

Example 4

An antimicrobial pigment was obtained in the same manner as in Example 2 except that lithium carbonate (Li ₂ CO ₃ ) was used instead of sodium carbonate in Example 2.

Example 5

100 g of a pigment obtained by mixing titanium dioxide and sericite in 1: 2 was dispersed in 100 ml of purified water, 13.0 g of silica (SiO ₂ ), 1.0 g of zinc oxide (ZnO), 2.0 g of calcium oxide (CaO), and aluminum oxide (Al ₂₎ O ₃ ) 2.0 g, sodium carbonate (Na ₂ CO ₃ ) 4.0 g, silver chloride (AgCl) 0.2 g, iron chloride (FeCl ₃ 6H ₂ O) 0.2 g of the paste phase was mixed well, concentrated ammonia water (28% Ammonia water ) 20 ml was added dropwise and stirred sufficiently to facilitate dissolution of silver chloride and titration of iron chloride. As the titration of iron chloride was completed, the paste phase turned into a cake phase, and when the ammonia odor was reduced, the surface was dried with hot air, completely dried at 110 ° C., and pulverized with a ball mill. This was slowly placed in a sintering furnace and roasted at 450 ° C. for at least 2 hours to completely remove chloride ions in the form of ammonium chloride (NH ₄ Cl). This was further heated at a rate of 10 ° C. per minute and treated at 780 ° C. for 2 hours to obtain an antimicrobial pigment.

Example 6

100 g of a pigment mixed with boron nitride and talc in 1:10 was dispersed in 100 ml of purified water in which 2.0 g of urea was dissolved, and was treated in the same manner as in Example 5 except that 0.4 g of zinc powder was used instead of silver chloride. An antimicrobial pigment was obtained.

Example 7

An antimicrobial pigment was obtained in the same manner as in Example 3 except that 0.3 g of copper sulfate was used in Example 3.

Example 8

To 100 g of a mixture of titanium dioxide and kaolin in a 1: 2 ratio, 8.5 g of silica (SiO ₂ ), 10.7 g of calcium carbonate (CaO ₃ ), 2.0 g of aluminum oxide (Al ₂ O ₃ ), and iron oxide (Fe ₂ O ₃ ) 0.5 g was mixed well and ground, to which 50 ml of 0.15% silver nitrate solution was sprayed to mix well. After drying at 120 ° C., 13.4 g of sodium silicate having a molar ratio of SiO ₂ / Na ₂ O of 2.4 and 50% of water (H ₂ O) content was added to 80 ml of purified water, and the mixture was sufficiently stirred and dried at 120 ° C. . The dried one was pulverized with a coarse grinder to loosen the aggregated particles, the temperature was raised at a rate of 10 ° C. per minute, and sintered at 800 ° C. for 1 hour to obtain an antimicrobial pigment.

Example 9

100 g of spherical silica having an average particle diameter of 5-10 µm was mixed with 10.5 g of amorphous silica fine powder, 5.0 g of calcium carbonate, 1.5 g of zinc carbonate, 1.2 g of aluminum oxide, and 0.4 g of yellow iron oxide (FeOOH), and ground to 0.3. 50 ml of% silver nitrate solution was sprayed to mix evenly. After drying at 120 占 폚, 10.0 g of sodium silicate having a molar ratio of SiO ₂ / Na ₂ O of 2.4 and 50% moisture (H ₂ O) content was added to 80 ml of purified water, and the mixture was sufficiently stirred and dried at 120 占 폚. . The dried one was pulverized with a coarse grinder to loosen the aggregated particles, the temperature was raised at a rate of 10 ° C. per minute, and sintered at 850 ° C. for 1 hour to obtain an antimicrobial pigment.

[Test 2 of antibacterial effect]

The antimicrobial effect of the antimicrobial pigments obtained in Example 5, Example 7, Example 8 and Example 9 was measured by measuring the minimum growth inhibitory concentration and the minimum bactericidal concentration. After incubation by inoculating the inoculum bacterial solution into the liquid and solid medium to which each sample was added at an arbitrary concentration, the growth of the microorganisms was prevented or sterilized as the minimum growth inhibitory concentration and the minimum bactericidal concentration. The strain used was the same strain as the antibacterial effect test 1, and the medium for enrichment was S. aureu s, E. coli, P. aeruginosa and Nutrient broth of Difco. Candida (C. albicans) used Sabouraud dextrose broth and black mold (A. niger) used Potato dextrose agar. The inoculum for inoculation of Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa was incubated at 37 ° C. for 18 hours in enrichment medium, and then inoculated in a liquid medium of 30 µl concentration at 37 ° C. for 24 hours in agar medium. It was. Candida was incubated at 30 ° C. for 24 hours in an enrichment medium, and then inoculated in a liquid medium having a predetermined concentration of 30 μl. The sensitive medium was incubated at 30 ° C. for 24 hours in agar medium. The black mold was incubated in sterile physiological saline after incubation at 25 ° C. for 5 days in an enrichment medium, and 50 μl each was plated on agar plate medium at a constant concentration, and the cultured at 30 ° C. for 72 hours was used as a susceptibility measurement medium. . The experimental results are shown in Table 2 to Table 6.

The dissolution test of the antimicrobial metal to the antimicrobial cosmetic pigments prepared in Examples 5, 7, 8 and 9 were carried out as follows.

Dissolution test of antimicrobial metal

After dispersing the antimicrobial pigment prepared in each example 2.0% in purified water and stirring for 5 minutes, and then left for 10 days, 20 days, 30 days, 50 days, 70 days, 90 days, the elution concentration of silver and copper of each sample Was measured by ICP (Inductive Coupled Plasma, France, JOBIN YVON Co.) is shown in Table 7 below.

The antimicrobial pigments of the present invention from the results of Table 7 show that antimicrobial metals are not detected over a long period of time or are eluted at very low concentrations (ppb units) to show a continuous antimicrobial effect.

[Example 10 and Comparative Examples 1 to 2]

Liquid Foundation

Next, the aqueous phase was warmed to 80 ° C. and stirred for 5 minutes according to the composition of Table 8, the pigment was added to the dispersion, and stirred at 4000 rpm. The oil phase part preheated to 80 degreeC was added here, and it stirred for 10 minutes at 3800 rpm, and cooled slowly, and prepared liquid foundation.

[Example 11 and Comparative Examples 3 to 4]

pack

Next, the raw materials 1 to 8 were dissolved and mixed at 80 ° C. according to the composition ratio of Table 9, and the raw materials 9 to 10 were added and emulsified. 11 to 13 raw materials were added and stirred, and the raw materials of 14 were dispersed in purified water, and 15 to 16 raw materials were added and mixed to prepare a pack.

Preservative experiments were carried out on the products prepared in Examples 10 and 11 and Comparative Examples 1 to 4 as follows.

Antiseptic test of the product

50g of each product was placed in the product container, and E. coli, S. aureus, and P.aeruginosa were incubated at 37 ° C in Nutrient agar for 24 hours, and then suspended in sterile saline, and C. albicans and A. niger were Potato. After incubation at 30 ° C. for 48 hours and 4 days in dextrose agar, the cells were inoculated at 10 ⁶ cells / g in suspension in sterile saline to measure the bacterial counts over time. The results are shown in Table 10 below.

In addition to the cosmetics as described above, the antimicrobial cosmetic pigments of the present invention include lotion, lotion, cream, sunscreen cream, two-way cake, powder foundation, complex, eye shadow, powder blush, face powder, baby powder, body powder, lipstick, lip Gross, lip pencil, eyeliner, eyebrow pencil, mascara, emulsified foundation, makeup base showed the same excellent antibacterial effect.

As described above, the antimicrobial cosmetic pigments according to the present invention exhibit an excellent antimicrobial effect, and the cosmetics containing the same have excellent antibacterial effect against the inoculated microorganisms than the cosmetics containing the conventional preservatives as well as excellent stability and sustained antiseptic effect. Safety was shown. Therefore, it can be used as an inorganic preservative excellent in skin safety in all the products containing cosmetic pigments.

Claims (23)

An antimicrobial cosmetic pigment, characterized by forming an amorphous glassy metal oxide composite coating layer on the surface of an inorganic pigment for cosmetics, and simultaneously incorporating and solidifying an antimicrobial metal or metal ion in the metal oxide composite coating layer skeletal structure. The antimicrobial cosmetic pigment according to claim 1, wherein the inorganic pigment for cosmetics has an average particle diameter in the range of 0.1-50 mu m. The inorganic pigment of claim 1, wherein the inorganic pigment is silica, talc, kaolin, mica, sericite, aluminum oxide, barium sulfate, zinc oxide, titanium dioxide, zirconium oxide, aluminum hydroxide, boron nitride, magnesium silicate, aluminum silicate, magnesium aluminum silicate. Cosmetic pigments, characterized in that one or two or more inorganic pigments selected from the group consisting of magnesium oxide, iron oxide, chromium oxide and chromium hydroxide. The metal oxide for forming a composite coating layer of a metal oxide on the surface of the inorganic pigment as a main component of silica alone or other than zinc oxide, magnesium oxide, calcium oxide, aluminum oxide, lithium oxide, oxide Antimicrobial cosmetic pigments, characterized in that one or two or more selected from the group consisting of sodium, potassium oxide and iron oxide. The method of claim 4, wherein the content of the metal oxide is at least 40.0 parts by weight of silica, zinc oxide, magnesium oxide, calcium oxide, respectively, or 0-20.0 parts by weight of aluminum oxide, 0-20.0 parts by weight of aluminum oxide, lithium oxide, An antimicrobial cosmetic pigment, characterized in that sodium oxide and potassium oxide are 0-15.0 parts by weight or a mixture thereof, and 0-3.0 parts by weight of iron oxide. The antimicrobial cosmetic pigment according to claim 1, wherein the coating amount of the metal oxide composite coating layer is 3.0-50.0 parts by weight based on the inorganic pigment. The antimicrobial cosmetic pigment according to claim 1, wherein the antimicrobial metal is selected from at least one of silver, copper and zinc. The antimicrobial cosmetic pigment according to claim 1, wherein the amount of the antimicrobial metal to be mixed is 0.00001 to 5.0 parts by weight based on the metal oxide composite coating layer. The surface of the inorganic pigment was coated with silica only by neutralization titration method of sodium silicate or sol-gel method using silane alkoxide, and then other metal oxides to be coated were filtered or dried by dry mixing or wet mixing, followed by sintering by heat treatment. Alternatively, both inorganic pigments and metal oxides to be coated are dry mixed or wet mixed simultaneously, filtered, dried and sintered by heat treatment to form an amorphous glassy metal oxide composite coating layer on the surface of the inorganic pigment, and the antimicrobial metal is coated with silica. Or a method for producing an antimicrobial cosmetic pigment, characterized in that by adding in the mixing step or sintering treatment step of metal oxide mixed solution. 10. The method of claim 9, wherein the neutralization titration method of sodium silicate for coating the silica is 60-80 DEG C while dispersing and stirring sodium silicate having a molar ratio of SiO ₂ / Na ₂ O in the range of 1-4 with an inorganic pigment in an aqueous phase. After heating to the temperature of (Acid Solution) gradually dropping the precipitate is adsorbed on the surface of the inorganic pigment as the end point, and the resulting precipitate is treated by filtration, washing, drying Method for producing a pigment for cosmetics. 10. The sol-gel method using silane alkoxide according to claim 9, wherein the sol-gel method, together with the silane alkoxide, adds an alcohol solution and an acid solution having the same carbon number as the carbon number of the alkyl chain bonded to the silane alkoxide to the water phase, Method of producing a pigment for antimicrobial cosmetics, characterized in that the pigment is dispersed and stirred and heated to a temperature of 25-80 ° C. to give a sol-gel reaction, and then left to stand for 30 minutes to 1 hour, followed by filtration, washing and drying. . The method for producing an antimicrobial cosmetic pigment according to claim 11, wherein the silane alkoxide is selected from one group consisting of tetramethoxysilane, tetraethoxysilane and tetrabutoxysilane. The coating amount of silica according to any one of claims 10 to 12, wherein the coating amount of silica by neutralization titration of sodium silicate or sol-gel method of silane alkoxide which first coats only silica on the surface of the inorganic pigment is 1.0-to the inorganic pigment. 15.0 parts by weight of the antimicrobial cosmetic pigment production method. 10. The method of claim 9, wherein the antimicrobial metal is added in the form of a metal itself or in a fine powder or in a metal saline solution. 15. The method according to claim 14, wherein when the aqueous metal salt solution is added, an inorganic pigment or a coated inorganic pigment is dispersed in an aqueous phase or an aqueous solution in which the metal salt is dissolved during wet mixing is added, and titrated with an alkaline aqueous solution to titrate the added metal salt. Method for producing a pigment for antimicrobial cosmetics characterized in. 10. The method according to claim 9, wherein the sintering treatment is performed at a temperature of 400-1200 ° C for 10 minutes to 10 hours. 17. The method according to claim 9 or 16, wherein the aqueous urea solution is subjected to neutralization titration of sodium silicate or sol-gel method of silane alkoxide or wet mixing or before sintering to control the atmosphere inside the sintering furnace during heat treatment. Method of producing a pigment for antimicrobial cosmetics, characterized in that the addition through the addition step. 18. The method of claim 17, wherein the amount of urea added is 0-0.3 parts by weight based on the coated inorganic pigment to be sintered. 17. The method according to any one of claims 9 to 12 and 14 to 16, wherein a small amount of ammonia water is added to react the anion for the purpose of removing the halogenated anion of the acid solution and the metal salt used, followed by drying and heat treatment. Method of producing a pigment for antimicrobial cosmetics, characterized in that to remove by roasting at a temperature range of 300-500 ℃. 20. The antimicrobial cosmetic pigment according to claim 19, wherein the ammonia water is used in an amount of 1: 1 equivalent based on the acid solution and metal salt used or 0-10.0 parts by weight of the inorganic pigment coated with ammonia water. Manufacturing method. Forming an amorphous glassy metal oxide composite coating layer on the surface of the inorganic pigment for cosmetics and at the same time containing an antimicrobial cosmetic pigment prepared by sintering by incorporating a solid solution of antimicrobial metal or metal ions into the skeleton structure of the metal oxide composite coating layer. Cosmetic composition characterized in that. The cosmetic composition according to claim 21, which contains 0.001-50.0 parts by weight of an antimicrobial cosmetic pigment. 23. The cosmetic according to claim 21 or 22, wherein the cosmetics include lotion, lotion, cream, pack, sunscreen cream, two-way cake, powder foundation, compact, eye shadow, powder blush, face powder, baby powder, lipstick, lip gloss, Cosmetic composition, characterized in that the lip pencil, eyeliner, eyebrow pencil, mascara, emulsified foundation, makeup base, liquid compact.